N-substituted-2,6-dinitro-3-(alkoxy or alkylthio)-4-substituted-aniline compounds

ABSTRACT

N-Substituted 2,6-dinitro-3-alkoxyanilines having a halo, lower alkyl, or trifluoromethyl substituent at the 4-position. The compounds are useful as pre- or post-emergence herbicides and can be formulated with the usual herbicide carriers.

United States Patent [1 1 Strong et al.

[4 Oct. 9, 1973 N-SUBSTITUTED-2,6-DINlTRO-3-(ALKOXY ALKYLTHIO)-4-SUBSTlTUTED-ANILINE COMPOUNDS [75] Inventors: Philip L. Strong; DonL. Hunter,

both of Anaheim; Cecil W. Le Fevre, Tustin, all of Calif.

[73] Assignee: United States Borax & Chemical Corporation, Los Angeles,Calif.

[22] Filed: Aug. 5, 1970 [21] Appl. No.2 61,428

[56] References Cited UNITED STATES PATENTS 3,403,180 9/1968 Soperu260/577 3,257,190 6/1966 Soper 260/577 X 3,518,076 6/1970 Wright 71/121X 3,546,295 12/1970 Maravetz.. 260/577 3,322,525 5/1967 Martin 71/983,119,736 1/1964 Clark et a1. 260/577 X Primary Examiner-Lewis GottsAssistant Examiner-C. F. Warren Attorney-James R. Thornton [57] ABSTRACT.N-Substituted 2,6-dinitro-3-alkoxyanilines having a halo, lower alkyl,or trifluoromethyl substituent at the 4-position. The compounds areuseful as preor postemergence herbicides and can be formulated with theusual herbicide carriers.-

11 Claims, No Drawings NSUBSTITUTED-2,6-DINlTRO-3-(ALKOXY OR ALKY THro-4-sUBsTrru Eu-A1vrLnvE coMPouNns This invention relates to novel alkoxysubstituted dinitroaniline compounds which are particularly useful asherbicides.

According to the present invention, there are provided novel compoundsof the formula in which R represents alkyl of at least two carbon atoms,alkenyl, alkynyl or aryl, R represents hydrogen, alkyl, alkenyl, oralkynyl, R is lower alkyl of up to six carbon atoms, Y is oxygen orsulfur, and Z represents lower alkyl, halo or trifluoromethyl. Also R-R, can represent a portion of a cyclic group such as an alkylene chainto form a heterocyclic group containing carbon atoms in addition to thenitrogen atom which is the point of attachment to the aromatic ring.

Typical examples of organic groups represented by R and/or R as definedabove are the lower alkyl, lower alkenyl, and lower alkynyl groupshaving up to about eight carbon atoms including the cyclic analogsthereof as well as the halo, hydroxy and lower alkoxy substitutedderivatives thereof. Typical examples of aryl groups which can berepresented by R are the monocyclic aryl groups such as phenyl and thesubstituted phenyls having one or more halo, lower alkoxy or lower alkylsubstituents. Thus, R and/or R, can be:

alkyl haloalkyl hydroxyalkyl lower alkoxyalkyl alkenyl haloalkenylhydroxyalkenyl lower alkoxyalkenyl alkynyl haloalkynyl hydroxyalkynyllower alkoxyalkynyl phenyl halophenyl lower alkylphenyl loweralkoxyphenyl in which alkyl, alkenyl and alkynyl have up to eight carbonatoms. I

Representative R and/or R groups are methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyL sec-amyl, n-pentyl, 3-pentyl, n-hexyl, 2-ethylhexyl,allyl, 2- butenyl, 2-butynyl, 3butynyl, methallyl, Z-pentynyl,2-hydroxyethyl, Z-bromoethyl, Z-methoxyethyl, 3- ethoxypropyl,2,2-dimethoxyethyl, 2-chloroallyl, 3- chloropropyl, 4-chloro-2-butynyl,4-hydroxy-2- butynyi, l-methyl-Z-methoxyethyl, propynyl, 2- bromoallyl,4-chloro-2-butenyl, 4-bromo-l-butenyl, 3-iodo-2-pentenyl, cyclopropyl,cyclopentyl, cyclo hexyl, 2-chlorocyclohexyl, cyclohexenyl phenyl, 3-chlorophenyl, 3-fluorophenyl, 4-methoxyphenyl, 2,4- dimethoxyphenyl,4-methoxy-2-butynyl, 2,4-

f\ N R4 \J in which R, is an alkylene group having from about two to sixcarbon atoms in the chain and optionally containing other atoms such asoxygen and nitrogen. Such linkages include the dimethylene,trimethylene, tetramethylene, diethyleneoxy, diethyleneimino, andhexamethylene groups.

Examples of lower alkyl groups represented by R include methyl, ethyl,n-propyl, isopropyl, n-butyl, amyl and n-hexyl. As pointed out above, Zcan also represent lower alkyl of up to about six carbon atoms,trifluoromethyl, or halo such as bromo, chloro, fluoro and iodo.

A preferred class of compounds according to this invention are those inwhich R is alkyl of two to six carbon atoms and R is hydrogen or alkylof one to six carbon atoms, the total number of carbon atoms for R, R,being about four to eight, R is alkyl of one to about three carbonatoms, Y represents oxygen, and Z is tri fluoromethyl.

The dinitroanilines of this invention are readily prepared by reactionof the corresponding 3-halo-2,6- dinitroaniline with an alkali metalalkoxide or thioalkoxide according to the following equation N N I N02-N02 N02 N RaYM MX l Z Z in which R R R Y and Z have the significancepreviously assigned, X represents a reactive halogen atom such asbromineor chlorine and Mvrepresents an alkali metal such as sodium orpotassium.

The reaction takes place by combining approximately equimolar amounts ofthe reactants at a temperature of from about room temperature to aboutC. Preferably a solvent such as an alcohol is employed in order tocontrol reaction temperatures and facilitate handling of the reactants.The insoluble by-product metal halide is readily separated from thereaction mixture such as by filtration and the desired product isolatedand purified by conventional procedures. The desired compounds areeither high-boiling liquids or crystalline solids which can berecrystallized froma suitable solvent, such as an alcohol. I

The alkali metal alkoxide or thioalkoxide is prepared by well-knownprocedures such as by addition of metallie sodium or potassium to theselected alcohol or thiol. The intermediate 4-substituted 3-halo-2,6-dinitroaniline can be prepared by reaction of at least an equimolaramount of anorganic amine with the corresponding 4-substitutedl,3-dihalo-2,6-dinitrobenzene in the presence of a solvent such as ahydrocarbon or alcohol. Preferably, about 2 moles of the amine is usedfor each mole of the dihalodinitrobenzene, the second mole of amineneutralizing the by-product hydrogen halide as it is formed.Alternatively, a tertiary amine can be used as the acid neutralizingagent. The reaction can be carried out in a sealed reaction vessel suchas an autoclave or at atmospheric pressure in the presence of a solvent.A reaction temperature in the range of from about 20 to about 100 C.preferably is employed to give good yields of the desired product and asatisfactory rate of reaction. The by-product amine hydrohalide isremoved by washing with water or by filtration from the solvent in whichit is insoluble. The desired product is isolated and purified bywell-known procedures such as by recrystallization.

The 4-substituted l,3-dihalo-2,6dinitrobenzene starting materials arereadily prepared by nitration of the corresponding 1,3-dihalobenzenewith a mixture of fuming nitric and fuming sulfuric acids at atemperature below about 80 C.

An alternate method for preparing the alkoxydinitroanilines of thisinvention comprises the amination of the corresponding 6-substitutedl,3-dialkoxy-2,4-

dinitrobenzene. About equimolar amounts of the selected organic amineare reacted with the dialkoxybenzene in a sealed reaction vessel at anelevated temperature. The alkoxy substituent between the nitro groups ispreferentially displaced by the amine to give the desired monoalkoxyaniline.

The following examples illustrate the preparation of representativecompounds of the present invention.

EXAMPLE I N-isopropyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline A200 ml. round-bottomed flask. equipped with a magnetic stirrer andreflux condenser was charged with 5.0 g. (0.0152 mole) ofN-isopropyl-3-chloro-2,6- dinitro-4-trifluoromethylaniline and 50 'ml.of anhydrous methanol. To this stirred solution was added 3.77 g.(0.0152 mole) of a 21.8% methanolic sodium methoxide solution. Onaddition, the mixture became a very deep red color. The mixture wasstirred at room temperature for 6 hours and was then heated at refluxtemperature for 18 hours. During this time the solution became a lightorange color and a small amount of white solids had precipitated. Themethanol was stripped from the reaction mixture on a rotary evaporatorleav-' ing an orange semi-solid residue. To this residue was added 100ml. of hexane and the mixture was refluxed with stirring for one hour todissolve product away from sodium chloride and any otherhexane-insoluble materials. The mixture was cooled somewhat andfiltered. The insoluble solids were washed with hexane and the filtrateswere evaporated to an orange oil which slowly crystallized on standingat room temperature. This residue was dissolved in 25 ml. of refluxing95% ethanol, and on standing, the product crystallized to give 3.46 g.(70.5%) ofa yellow crystalline solid; mp. 55.557 C. Afterrecrystallization from 95% ethanol, the product melts at 54.555.5 C.

EXAMPLE ll N,N-di-n-propyl-2,6-dinitro-3-rnethoxy-4-trifluoromethylaniline The compound was prepared in a similarmannerreaction of N,N-di-mpropyl-3-chloro-2,6-dinitro-4.trifluoromethylaniline with sodium methoxide in anhyl drous methanol.The product was obtained. in 80.5% yield as a slightly viscous, red oil.I

' EXAMPLE n1 N,N-diethyl-2,6-dinitro-3-methylthio-4-trifluoromethylaniline A solution of sodium methylmercaptide wasprepared by adding 0.25 g. (0.01 1 mole) of sodium to 5.30 g. (0.011mole) of 10% methyl mercaptan in ethanol and stirring until the sodiumhad all reacted. The resultant solution was then added dropwise to 3.42g. (0.01 mole) of N,N-diethyl-3 -chloro-2 ,6-dinitro -4-trifluoromethylaniline in 25 ml. of dry ethanol. The resultant mixturewas stirred at room temperature for 20 hours. The solvent was removed bydistillation under reduced pressure and the residue was then dissolvedin 100 ml. of ether and filtered. Evaporation of the ether gave a solidresidue which was recrystallized from absolute ethanol to give 2.17 g.(62%) of the desired product as an orange solid, rn.p. 67.569 C.

EXAMPLE IV N,N-di-n-propyl-2,6-dinitro-3-hexyloxy-4-trifluoromethylaniline A solution of n-hexyl alcohol sodium salt wasprepared by heating 0.23 g. (0.0] mole) of sodium in 25 ml. of n-hexanolat reflux temperature for 15 hours. This solution was added to asolution of 3.70 g. (0.01 mole) N,N-di-n-propyl-3-chloro-2,6-dinitro-4-trifluoromethylaniline in 20 ml. of hexanol. The resultant mixture wasstirred at room temperature for'6 hours and then at reflux temperatureovernight. The solvent was removed by use of a rotary vacuum evaporatorunder reduced pressure. The residue was extracted with boiling hexane.The hexane extract was evaporated to give a residue which was dissolvedin absolute ethanol, filtered and again stripped of solvent underreduced pressure to give 3.69 g. of ambercolored oil. The product wasidentified by its infrared and NMR spectra.

The following are among the many other compounds of this invention whichcan be prepared according to the procedures described above.

N-cyclohexyl-4-chloro-2,6-dinitro-3-methoxyaniline;

N,N-pentamethylene-4-chloro-2,6-dinitro-3- methoxyaniline; rn.p. 94-95.5C. N-ethyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; rn.p. 9898.5C.

N-sec-butyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; oil

N-tert. butyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; oil

N,N-diethyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; oil

N-methyl-N-n-butyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; oil

N-methyl-N-sec-butyl-Z,6-dinitro-3-methoxy-4- trifluoromethylaniline;oil

N-ethyl-N-n-propyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; oil

N-ethyl-N-isopropyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; oil

N-ethyl-2,6-dinitro-3-ethoxy-4- trifluoromethylaniline; rn.p. l04.5l06C. I N,N-diethyl-2,6-dinitro-3-ethoxy-4- 't'riflupromethylaniline; oilN-isec-bu'tyl-2,6-dinitro-3-ethoxy-4- 'triflu oromethylaniline; oil

N-( 3 -arnyl)-2 ,6-dinitro-3-ethoxy-4- trifluoromethylaniline; oilN-sec-amyl-2.6-dinitro-3-ethoxy-4- trifluoromethylaniline; oil'N,N-diethyl-Z,6-dinitro-3-isopropoxy-4- trifluoromethylaniline; oil N ,N,-diethyl-Z,6-dinitro-3-n-butoxy-4- trifluoromethylaniline; oilN-sec-butyl-2,6-dinitro-3-methylthio-4- trifluoromethylaniline; oilN,N-di-n-propyl-2,6-dinitro-3-methylthio-4- trifluoromethylaniline; m.p.8486 C. N-ethyl-2,6-dinitro-3-butylthio-4- trifluoromethylaniline; m.p.4648 C. N-sec-amyl-2,6-dinitro-3-n-hexylthio-4- trifluoromethylaniline;oil N,N-di-n-propyl-2,6-dinitro-3-ethoxy trifluoromethylaniline; oilN,N-pentamethylene-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; m.p.98-99 C. N-( l-methyl-2-methoxyethyl )-2,6-dinitro-3-methoxy-4-trifluoromethylaniline; 57.558.5 C.N-(2,2-dimethoxyethyl)-2,6-dinitro-3-methoxy-4- trifluoromethylaniline;m.p. 6364 C. N-n-hexyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline;oil N-ethyl-N-n-butyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline;oil N,N-diallyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; oilN-phenyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; m.p. l00l02 C.N-cyclohexyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; m.p.94.595 C. I N-cyclopropyl-2,6-dinitro-3-methoxy-4-trifluoromethylaniline; m.p. 62.5-63.5 C. N,N-diethyleneoxy-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; m.p.1l4l C. N-( 3-chloro-n-propyl)-2 ,6-dinitro-3-methoxy-4-trifluoromethylaniline; oil N,N-di-n-butyl-Z,6-dinitro-3-methoxy-4-trifluoromethylaniline; oilN,N-bis-(2-methoxyethyl)-2,6-dinitro-3-methoxy-4-trifluoromethylaniline; oil N-sec-amyl-2,6-dinitro-3-methoxy-4-trifluoromethylaniline; oil N-(3-pentyl)-2,6-dinitro-3-methoxy-4-trifluorornethylaniline; oilN-methyl-N-cyclopentyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline;oil 7 N-sec butyl-4-bromo-2,6-dinitro-3-methoxyaniline;

oil N,N-diethyl-4-bromo-2,6-dinitro-3-methoxyaniline;

oil N-sec'amyl-4-bromo-2,6-dinitro-3-rnethoxyaniline;

oil N-methyl-N-sec-butyl-4-bromo-2,6-dinitro-3 methoxyaniline; oilN,N-di-n-propyl-4-bromo-2,6-dinitro-3- -methoxyaniline; oilN-(3-chloro-n propyl)-4-chloro-2,6-dinitro-3- methoxyaniline; oil g N-(l-methyl-2-methoxyethyl)-4-chloro-2,6-dinitro- 3-methoxyaniline; oilN,N-di-n-butyl-4-chloro-2,6-dinitro-3- methoxyaniline; oil

hip.

6 N-sec-butyl-Z,6-dinitro-3-methoxy-4-methylaniline oilN,N-diethyl-2,6-dinitro-3-methoxy-4methylaniline;

oil N,N-di-n-propyl-2,6-dinitro-3-methoxy-4- methylaniline; oil

I EXAMPLE. v N-propargyl-2,6-dinitro-3-methoxy-4- trifluoromethylanilineA 25 ml. heavy-walled glass reaction tube was charged with 4.0. g.(0.0135 mole) of 2,4-dimethoxy-3,5- dinitrobenzotrifluoride, 0.74 g.(0.0135 mole) of propargylamine and about 20 ml. of dimethoxyethane. The

tube was sealed and allowed to stand at room temperature for 98 hoursfollowed by heating in an oven at 105 C. for 4 hours. The tube was thenopened and the contents transferred to a 250 ml. round-bottomed flask.The solvent was removed on a Rinco evaporator leaving a residual oilwhich crystallized on standing. The residue was dissolved in 25 ml. ofrefluxing 95% ethanol and, on cooling, the product crystallized. Thesolids were filtered and vacuum dried giving 1.77 g. 4l.l%) of a yellowcrystalline product; m.p. 8 l82.5 C. After recrystallization fromethanol, the product melts at 82.584 C.

EXAMPLE VI in a similar manner,2,4-dimethoxy-3,S-dinitrobenzotrifluoridewas reacted with2-hydroxyethylamine to give N-(2-hydroxyethyl)-2,6-dinitro-3-methoxy-4'-trifluoromethylaniline; m.p. l00.5l01.5 C.

EXAMPLE VII In a similar manner,2,4-dimethoxy-3,S-dinitrobenzotrifluoride was reacted withdiethanolamine to give N,- N-bis(2hydroxyethyl)-2,6-dinitro-3-methoxy-4- trifluoromethylaniline; m.p.l45l46 C.

The compounds of this invention are excellent herbicides and areespecially useful as selective herbicides for controlling weeds in thepresence of desirable crops, such as cotton and beans such as soybeans.

The compounds can be applied as both a preemergence or a post-emergencetreatment; that is they can be applied to soil in which the weeds willgrow or they can be used to kill or suppress the growth of weeds or tokill'or prevent the emergence of seedlings of undesirable plants. Thus,the alkoxyanilines can be used to control the growth of weedsby applyinga phytotoxic amount of one or more of the active compounds of thisinvention to the locus to be protected, that is, soil in which the weedsare growing or will grow or the foliage of the growing plants. Weeds asused herein is meant about 30 pounds of one or more of the activecompounds per acre is effective in controlling plant growth.

Preferably an application rate of from about 0.25 to about 6 pounds peracre is employed. At such rates the undesirable weeds are killed orstunted with little or no injury to desirable crops.

The following examples illustrate the herbicidal activity of typicalcompounds of this invntion.

EXAMPLE Vlll Greenhouse flats were planted to soybeans (SB), velvet leaf(VL), oats (O) and millet (M) and the flats sprayed on the same day asplanting with an ethanoldioxane solution of the compound to be tested ata rate of 5 pounds per acre.

Another set of flats with the same plats was treated after the plantshad emerged and were about 1 inch in height. These flats were alsosprayed with an ethanoldioxane solution of the compound to be tested ata rate of 5 pounds per acre. The flats were kept in the greenhouse andwatered when needed. 21 days after treatment the flats were examined andthe plants rated for herbicidal activity on a to 9 scale in which 0 noeffect, substantial injury with some kill, and 9 com-N,N-dicthyl-2,tl-dinitrn-3 mnthylthio-i-trilluoromothylanilincNisopropy1-2, initro-3- mvthoxyA-tritluoromethylaniline 0 3N,N-di-n-propyl-2,6-dinitro-3- methylthio-Ltrilluoromethylaniline 3 4 69 4 4 5 6 N,N-di-mpropyl-Z,6-dinitro-3- ethoxy-t-triiluoromethylanilintxO 3 5 Q 2 4 N(l-methyl-2-1nethoxycthyl)-2,G-dinitro-3-n1ethoxy-4-trifiuoromethylaniline 0N-methyl-N-cyt-lopcntyl-2,6-

dinltro-S-methoxyl-trifluoromethylanilino N'0tilyi-Nll-[il'ODYi-Llrdinilf0- 3-tncthoxy--triiluoromt'thylaniline. 3 3 (i ll 33 N-methyl-N-n-butyl-l,(l-dinitro-3-nicthoxy4-triflnoromcthylanilinvN,N-diallyl-2,6-dinitro-3- methoxyA-triiluoromethylaniline l 3 l 9 3 3 05 N-(3-pentyl)-2,6-dinitro-3- methoxyi-trifiuoromethylaniline. 4 7 7 9 44 3 9 N-sec-amyl-2,fi-dinitro-3- methoxy-atrilluoromethylaniline. 3 8 39 4 3 3 9 N,N-bis(2-methoxyethyl)-2,6-

dinitro-3-methoxy-44rifluoromethylaniline 1 5 2 9N-sec-hutyl-2,fi-dinitro-B- rncthylthio-i-tri{luoromcthylaniline 2 N (lmt-thylmethoxycthyD- 4-chloro-2,ll-rlinitr o-3- rnethoxyanillncN,N-diethyl-l-bromo-ltl' dinitro-B-mothoxyanilincN,N-di-iupropyl-ZiS-dinitro-S- rncthoxyA-mcthylanilineN-soc-butyl-Zddinitro-B- mcthoxy-i-methylanilincN-scc-butyl-i-brorno-Zedinitro-3-methoxyanilineN-socbutyl-2,6-dinitr0-3- ethoxy-l-trifiuoromethylanilineN-(3chloron-propyl)-2,6-

dinltro-Zi-methoxyA-chloroaniline CAI muse

enu:-

Iowa:

Applied at 25 pounds per acre.

NOTE: Some of the compounds were not included in the post-emergencetest.

EXAMPLE IX 1 the greenhouse and watered when needed. Twenty-two daysafter treatment the flats were examined and the plants rated forherbicidal activity as described in Example Vlll. The following resultswere obtained.

TAB LE 11 Activity Compound Plant specie:

Pigweed "'1 Velvet leaf Morning glory;

Compound A N-se c-butyl-2,6-dinitro-3-methoxy-4-trifiuoromethylanilino.

Compound B N,Ndiethyl-2,6-dinitro-3-methoxy-4-trifluoromethylaniline.

Compound CN,Ndl-ii-propyl-2,6-dinitro-3-methoxy-4trifluoromethylaniline.

EXAMPLE X The procedure of Example Vlll was followed except thecompounds to be tested were applied as a preemergence treatment at arate of IS pounds per acre. The following results were obtained.

Since a relatively small amount of one or more of the active aniiinesshould be uniformly distributed over the area to be treated, thecompounds preferably are formulated with conventional herbicidecarriers, either liquid or solid. Thus, the compounds can be impregnatedon or admixed with a pulverulent solid carrier such as lime, talc, clay,Bentonite, calcium chloride, vermiculite, and the like. Alternatively,the compounds can be dissolved or suspended in a liquid carrier such aswater, kerosene, alcohols, diesel oil, xylene, benzene, glycols,ketones, and the like. Since many of the compounds are oils, they arereadily formulated in solvents. A surfactant preferably is included toaid in dispersion, emulsification and coverage. The surfactant can beionic or nonionic, and may be a liquid or a solid. The use of the termsurfactant herein is intended to include such compounds commonlyreferred to as wetting agents, dispersing agents and emulsifying agents.Typical surfactants include the alkylarylsulfonates, the fatty alcoholsulfates, sodium salt of napthalenesulfonic acid, alkylaryl polyetheralcohols, long chain quaternary ammonium compounds, sodium salts ofpetroleum-derived alkylsulfonic acids, polyoxyethylenesorbitanmonolaurate, and the like. These dispersing and wetting agents are soldunder numerous trademarks and may either be pure compounds, mixtures ofcompounds of the same general group, or they can be mixtures ofcompounds of different classes. Surfactants can also be included incompositions containing a solid inert carrier.

Concentrated compositions containing the active agent which can besubsequently diluted, as with water, to the desired concentration forapplication to plants and soil are also provided. The advantages of suchconcentrates are that they are prepared by the manufacturer in a formsuch that the user need only mix them with a locally available carrier,preferably water, thereby keeping shipping costs to a minimum whileproviding a product which can be used with a minimum of equipment andeffort. Such concentrates may contain from about percent to about 99percent by weight of one or more of the active anilines with a carrieror diluent, which may be a liquid or a solid. Liquid carriers which aremiscible with the active agent or other liquids in which the compoundmay be suspended or dispersed can be used. A surfactant is alsogenerally included to facilitate such dilution or dispersion in water.However, the surfactant itself may comprise the carrier in suchconcentrates.

The herbicidal compositions can include other beneficial adjuvants, suchas humectants, oils and contact agents. Also, other herbicides such asthe sodium borates, sodium chlorate, chlorophenoxyacetic acids,

substituted uracils and ureas, triazines, benzimidazoles, carbamates,anilides, amides, and halo-alkanoic acids, can be included in theformulation.

Various changes and modifications of the invention can be made, and, tothe extent that such variations incorporate the spirit of thisinvention, they are intended to be included within the scope of theappended claims.

What is claimed is:

l. A compound of the formula RI R2 NO:- NO;

YRz

in which R, is lower alkyl of at least two carbon atoms, lowercycloalkyl, lower alkenyl, lower cycloalkenyl, lower alkynyl, ormonocyclic aryl and R is hydrogen, lower alkyl, lower cycloalkyl, loweralkenyl, lower cycloalkenyl, or lower alkynyl, said lower alkyl, lowercycloalkyl, lower alkenyl, lower cycloalkenyl and lower alkynyl groupshaving 0-2 halo, hydroxy or lower alkoxy substituents, said monocyclicaryl having 0-2 halo, lower alkoxy or lower alkyl substituents, R islower alkyl, Y is oxygen or sulfur, and Z is lower alkyl, halo, ortrifluoromethyl.

2. A compound in accordance with claim 1 in which R, is alkyl of two tosix carbon atoms, R, is hydrogen or alkyl of one to six carbon atoms, R;is alkyl of one to three carbon atoms and Y is oxygen, the total numberof carbon atoms represented by R, R being four to eight. v v

3. A compound in accordance with claim 2 in which Z is trifluoromethyl.

4. A compound in accordance with claim 2 in which Z is chloro.

5. A compound in accordance with claim 2 in which- Z is methyl.

6. A compound according to claim in which R and R are ethyl.

7. A compound according to claim 2 in which R and R are n-propyl.

8. A compound according to claim 2 in which R is hydrogen and R is3-pentyl.

9. N-sec-butyl-2 ,6-dinitro-3-methoxy-4- trifluoromethylaniline.

l0. N,N-di-n-propyl-2,6-dinitro-3-methoxy-4- trifluoromethylaniline.

11. N-( 3-pentyl)-2,6-dinitro-3-methoxy-4- trifluoromethylaniline.

2. A compound in accordance with claim 1 in which R1 is alkyl of two tosix carbon atoms, R2 is hydrogen or alkyl of one to six carbon atoms, R3is alkyl of one to three carbon atoms and Y is oxygen, the total numberof carbon atoms represented by R1 + R2 being four to eight.
 3. Acompound in accordance with claim 2 in which Z is trifluoromethyl.
 4. Acompound in accordance with claim 2 in which Z is chloro.
 5. A compoundin accordance with claim 2 in which Z is methyl.
 6. A compound accordingto claim 2 in which R1 and R2 are ethyl.
 7. A compound according toclaim 2 in which R1 and R2 are n-propyl.
 8. A compound according toclaim 2 in which R1 is hydrogen and R2 is 3-pentyl. 9.N-sec-butyl-2,6-dinitro-3-methoxy-4-trifluoromethylaniline. 10.N,N-di-n-propyl-2,6-dinitro-3-methoxy-4-trifluoromethylaniline. 11.N-(3-pentyl)-2,6-dinitro-3-methoxy-4-trifluoromethylaniline.